of carlisle



spt."21,1926; v A Re. 16,426 v A. H.A'DA V|ES Er Al..

' l 'l PRODUCTION on cQLogINevuA-TTERS roriginal Filed VNov. 14g-A1921 j l 30 tion products or 35 decomposed Reissued Sept. 241, 1926.

FRASER THOMSON AND JOHN THOMAS,

rOIE" WILLENHALL, ENGLAND; Bf MARY `or canLrsLn, ENGLAND, assrcxons ro SCOTTISH DYES, LIIITED,`0F CARLISLE, ENGLAND.A

PRODUCTION OF COLOBING MATTERS.

briginal n. 1,531,200, aatea'uarch 24, 192s, serial x0. 515,086, mea november 14 1921.

Application r for reissue led February 12, 1926. Serial No. 87,980.

This invention relates to the of coloring matters either as d es or intermediates for the production ofl yes.

It has for its objectvto provide improved i or new coloring matters. We have made a. large y number of experiments and have found, first, using isodibenzanthrone as a basis a classof bodies which class yield ox'- idation products, and second, that these oxy- '10 derivatives may be submitted to the processes of alkylation (including arylation and alphylation)' and acylaticn -and that the bodies in both cases, that is, either the oxidation products or the alkylv or acyl derivatives, can act as dyes or intermediates for the Ilroductionl of dyes. We have discovered ow to prepare these bodies and also how to app y them.

We have also found that the aforesaid oxidation products are capable of being reduced, but not necessarily back to the parent body, by such substances as sulphites.

Either the oxidation products or the reduced bodies can be made to yield under suitable conditions (examples of which are given below) acyl derivatives or alkyl de- `-rivatives', which bodies possess extremely valuable pro erties as dyestuffs.

We have a o found that either the oxidatheir alkylated or aeylated derivatives vcan form additive compounds with sulphuric acid. These can be used as production a means of isolating the required bodies as' these sulphuric acid compounds are readily on treatmentwith excess of water giving the oxidation products or their derivatives in a form suitable for use in further reactions o r themselves as dyestuis. The accompanying diagram represents in 40 a conventional manner what may be re arded as the constitutional formulael o Ilisodibenzanthrone, "the perylene ring; system being shown in heavy lines.

The invention in brief consists in the pro- 45'rduction` of coloring matters either as dyes or intermediates for the productionu of dyes `from isodibenzanthrone, namely, by its oxidation, that product of oxldation being suby brought to y Re. 16,426

WILLENHALL, ENGLAND, AND ROBERT .i

sequently mildly reduced and either of the i y bodies treated for the introduction'of organic radicl'es or inorganic radicles, particularly the alkyl derivative.

The followin 'examples are given to illustrate metho s for the production of oxidation products of the sub-class referred to above and their subsequent acylation or alkylation.

' y v Eample A.

10 parts-of isodibenzanthron are dissolved in 300 parts of strong sulphuric acid, along with 5 parts of crystalline boric acid. To the suspension isl then added 12 partsV of commercial manganese ty). The mixture is then raised to a temperature of C. for several hours. At the end of this time the product is isolated by pouring. into a large excess of water, the boil, and 20 parts of-sodium bisulphite added. The mixture is boiled for 1 hour and filtered. The yield is 28 parts of a greenishcoloredpaste. `For utilizing this past in one way, parts f the paste of the above described oxidation product are suspended in 150 parts of nitrobenzene, and 10 parts of sodium carbonate added. The water is then distilled oli and 10 parts of dimethyl sulphate added through a reflux condenser, after cool 150 C. The` mixture is boiled for several hours during which a blue color develops. When the reaction is complete a test portion dyes cotton blue shades, which are no longer sensitive to acid and alkali. matter may be isolated by removin the n1- trobenzene by steamy distillation, fo owed by ilteration and washing. The dyestul may be used in this form directly, or maybe submitted t o further purification. i

'Example Bi.y

' 25 parts of the pasteofthe oxidation r0- duct from isodibenzanthrone descri in Example A containin 5 parts of solid and 10 parts of sodium car nate are mixed with 150 parts of nitrobenzene ing to` and the water,dis.

The coloring V reux condenserl -j mixture 40 p huric acid of the saine The purit tilled olf. 10 parts of dimeth l sulphatea're 'then added and the mixture oiled under a untill a test portion :when dyed on cotton shows the alkylation to be I complete; which is the casewhe/n the test d eings are not'changed in shade by acld or a kali. vThe pro ess of the reaction may be followed by't e color of the suspension, which at first is red-,violet in color, and l changes to greenish-blue. The methylated product may -be isolated by filterin the hot nitrobenzol `solution and washing t e precipitate withjhot nitrobenzenenntilall the dyestuf is removed; the

- l liltrates a're concentrated and `the product allowed to crystallize. It separates` in the form of a dark crystalline powder. This powder disolves in strongdsulphurlc acid with a green color which orf`y dilution yields I0 a greenish-blue paste. It dissolves in alkalineL lhydrosulphite with a blue color, and

dyes cotton from the vat blue shades, which on oxidation become greenish-blue. These yshades are fast .to the action of acids, chlo'- il rinefand Soaping treatment. i

Example 0'. The oxidation product of isodibenzani throne Imay be puriedbytreatment with `80 strong sulphuric acid in the manner described parts of the oxidation roductA of isodi- Vbenzanthrone in the state o fine powder are dissolved in 4 00 parts of strong sulphuric acid at 60 C. The correct amount of water is ynow added to the 'solution to reduce' the concentration of the sulphuric acid to 85%. After allowing to stand for 12 hours the is filtered and washed with sulstrength.v The preclpitate consists of a pure form of the oxidation product, and is worked up by dlpting with water, iling'u reducing with sodium bisulphite and ltering.

of the product can be demonstrated by e tests, and ,it is found that shades are o tained of a blue gray color, considerably more brilliant and intense than can be obtained from the crude product. The acid iltrates contain a further quantity of considerably less pure oxidation product.` The shades obtained from the latter are considerably duller and weaker.

u f Eample D. l

`To typif the action of other agents on t zanthrone, given .i

5 parts of the oxidation product of isodibenzanthrone are suspended in parts of nitrobenzene and 5 arts of diphenyl dichlormethaneaare addld. I'

alkylating e oxidation product of isodifbenthe following examples are The solution on boilingassumes aA blue 5 color, and hydroch1oricacid)V is evolved.

. both vWhen the latteraceases the color is worked up by the method of Example II of cop'ending application No. '515,08

The product is obtained after crstallizing f as a dark crystalline powder, whic dissolves in strong sulphuric acid with an emerald green color, ,giving on dilution a ra sulphate, and on further dilution a ul blue paste. It dissolves in alkaline `hydrosulphite solution with a blue color, and dyes cotton blue shades, which on oxidation and washing become reddish blue.

These shades are fast to the action of acids andalkalies, and to bleaching and light.

In the preparation ofthe oxidation roducts of isodibenzanthrone we vhave mentioned the use of manganese dioxide and sulphuric acid, 'but other oxidizing vagents such as nitric acid can be `employed with suitable results.' Isodibenzanthrone may also be nitrated, reduced, diazotized and boiled to form `an oxy compound which behave inthe manner describe We have vgenerally speaking found the reaction to proceed more rapidly and smoothly with the reduced derivatives than with the crude oxidation product but the alkylated or acylated products appear to be the same in cases. H aving no`w `described our invention what we claimI as new Letters- Patent is z'- 1. The process of producing colorin matters of the y'anthraquinone series-.'whic consists in the oxidation of isodibenzanthrone and the partial reduction of the 'product' followed bythe introduction of an organic radicle. v

2. The processof producing coloring matters of the anthraquinone series which cons'ists in the oxidation of isodibenzanthrone and thev artial reduction of the productA followed radicle.

3. The process of producingcolorin matters of the anthraquinone series whic cony the. introduction of an alkyl `sists in theoxidation of isodibenzanthrone and the partial reduction of the product followed by the introduction of an a l radicle, the product being subsequent y treated with strong sulphuric .aci

4. A process for the .regeneration of an which includes the step of' sulphuric acid com ound an samewith excess o water.

'reparing the treating the 5. VAn oxidation compound of isodibenzanthrone. f y f 6.Y As a newv article of manufacture the coloring matter ofthe anthraquinone series and desire to secure by lao s obtained by oxidizing isodibenzanthrone and subs uently reducingthe product.

7. s a new article of manufacture the coloring matter of the 'anthraquinone' series ola/tained by oxidizing isodibenzanthrone, re-

'obtain v duoing the roduct and introducin anorgenie ndic g therein. c

8. As a new article of manufacture the oolorin matter of the anthraquinone series by oxidizing isodbenzanthrone reducing the product and introducing an aikyl radiale therein. f

In testimony whereof we have signed our names to this s iiication.

MARY OLIVIA DAVIES, Adminiatratri of Arthur Hugh Davies, deceased.

ROBERT FRASER THOMSON. J. THOMAS. 

